JP3921524B2 - Organophosphorus compound having polyethylene glycol structure and hydroformylation reaction catalyst using the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel organophosphorus compound useful as a ligand for organic synthesis reactions using water as a solvent, and a hydroformylation water-soluble catalyst comprising this and a Group 8 transition metal complex.
[0002]
[Prior art]
Conventionally, various water-soluble ligands used as a catalyst for hydroformylation reaction have been developed. Typical examples include 3,3 ', 3 "-phosphinidine tris (benzenesulfonic acid) sodium salt, 4,4'-(phenylphosphinidene) bis (benzenesulfonic acid) potassium salt, diphenylphosphine. And finobenzoic acid ("Aqueous catalysts for organic reactions" B. Cornils, E. Wiebus, Chemtech, 25, 33-38 (1995)).
[0003]
A catalyst obtained by mixing these organophosphorus compound ligands with a metal complex such as a rhodium complex activates a hydroformylation reaction using propene or the like which is soluble in water as a raw material olefin, and this catalyst is used in the reaction system. Since it exists in the aqueous layer, it has the feature that it can be easily separated from the product dissolved in the oil phase.
[0004]
However, these ligands have a drawback in that their catalytic activity is remarkably reduced in hydroformylation reactions using water-insoluble olefins such as 1-octene and 1-dodecene which are long-chain alkenes as raw materials ( T. Bartik, BB Bunn, B. Bartik, BE Hanson, Inorg. Chem., 33, 164 (1994)).
[0005]
In order to solve this problem, a method has been proposed in which a long chain alkylamide or cyclodextrin is added as an additive to the catalyst composed of the above ligand and rhodium complex to facilitate the reaction (MJH Russell, Platinum Met. Rev., 32, 179 (1988). E. Monflier, G. Fremy, Y. Castanet, A. Mortreux, Angew. Chem. Int. Ed. Engl., 34, 2269 (1995)).
However, this method requires a complicated operation to remove the above-mentioned additive when isolating the product, and lacks practicality.
[0006]
[Problems to be solved by the invention]
The present invention has been made in view of the circumstances as described above. The first object of the present invention is to smoothly convert these olefins even if water-insoluble olefins are used as raw materials for the hydroformylation reaction. A second object of the present invention is to provide a novel organophosphorus compound useful as a ligand for a catalyst capable of hydroformylation. A second object is to provide a hydroformylation reaction catalyst comprising such an organophosphorus compound and a Group 8 transition metal complex. It is to provide.
[0007]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors use a specific amphiphilic organophosphorus compound having a water-soluble structure and a lipophilic structure in one molecule as a ligand, and It has been found that a catalyst combined with a genus transition metal complex smoothly promotes a hydroformylation reaction of an olefin insoluble in water, and has completed the present invention.
That is, according to the present invention, the following inventions are provided.
1. The following general formula (1)
R ¹ R ² PA (CH ₂ ) _n (OCH ₂ CH ₂ ) _m R ³ (1)
(Wherein R ¹ and R ² represent an alkyl group, an aryl group, an aralkyl group, an alkoxy group or an aryloxy group, R ¹ and R ² may be bonded to form a ring, R ³ is , A hydroxyl group and a lower alkoxy group, A represents a phenylene group or a methylene group, n represents 5 to 30, and m represents 3 to 300).
2. A hydroformylation reaction catalyst comprising an organophosphorus compound represented by the general formula (1) and a Group 8 transition metal complex.
3. 3. The hydroformylation reaction catalyst according to 2 above, wherein the organophosphorus compound represented by the general formula (1) is liganded to a Group 8 transition metal complex.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The organophosphorus compound of the present invention is a novel compound not described in any literature, and as is apparent from the chemical structural formula represented by the general formula (1), the phosphorus atom and the polyethylene glycol hydrophilic moiety are hydrophobic groups. It is a compound exhibiting amphipathicity bonded through a certain long-chain alkylene group or long-chain alkylenephenylene group.
The reason why the ligand according to the present invention promotes the hydroformylation reaction has not been clearly clarified yet, but (1) it has a hydrophilic group at one end of the molecule as apparent from the structural characteristics of the compound. However, since it has a phosphorus atom that coordinates the catalyst at one end of the hydrophobic group, the catalyst tends to exist toward the organic layer in the reaction system, and (2) this compound is at the reaction temperature of the hydroformylation reaction. Then, it is conceivable that the solubility in water becomes low and the organic layer tends to exist on the organic layer side.
[0009]
R ¹ and R ² bonded to the phosphorus atom in the general formula (1) represent an alkyl group, an aryl group, an aralkyl group alkoxy group or an aryloxy group, and R ¹ and R ² are bonded to form a ring. It may be formed. This alkyl group includes both a chain and a ring. Carbon number of an alkyl group is 1-10, Preferably it is 1-6. Specific examples of the alkyl group include, for example, methyl group, ethyl group, butyl group, hexyl group, cyclohexyl group and the like.
[0010]
Aryl groups include both aryl groups consisting of carbocycles and aryl groups consisting of heterocycles. In this case, examples of the carbocyclic ring include condensed rings such as a naphthalene ring, an indene ring, an anthracene ring, and a phenanthrene ring in addition to a benzene ring and a biphenyl ring. On the other hand, examples of the heterocyclic ring include five-membered rings such as furan, thiophene, oxazole, and thiazole; and six-membered rings such as pyridine, pyridazine, pyrimidine, and pyrazine. Moreover, this aromatic ring may have various substituents. Examples of such substituents include various types containing heteroatoms such as oxygen atom, nitrogen atom, silicon atom, and halogen atom, such as methoxy group, dimethylamino group, trimethylsilyl group, trifluoromethyl group, chlorine, fluorine and the like. Can be mentioned. Specific examples of the aryl group include phenyl, tolyl, dimethylaminophenyl, anisyl, chlorophenyl, fluorophenyl, trifluoromethylphenyl, naphthyl, pyridyl, and furyl groups.
[0011]
Examples of the aralkyl group include a benzyl group and a phenylethyl group. Moreover, as an alkoxy group and an aryloxy group, it has C1-C10, You may have various substituents containing hetero atoms, such as an oxygen atom, a nitrogen atom, a silicon atom, and a halogen atom. Examples of such alkoxy groups and aryloxy groups include methoxy group, ethoxy group, butoxy group, hexyloxy group, phenoxy group, methylphenyloxy group, butylphenyloxy group, fluorophenyloxy group and the like.
[0012]
Examples of R ¹ and R ² being combined to form a ring include tetramethylene, pentamethylene, dimethylenedioxy, trimethylenedioxy, dimethyldimethylenedioxy, and tetramethyldimethylenedioxy groups. , Dipropyldimethylenedioxy group, diphenyldimethylenedioxy group, tetramethyltrimethylenedioxy group, phenylenedioxy group, diphenylenedioxy group and the like.
[0013]
R ³ in the general formula (1) represents a hydroxyl group or a lower alkoxy group. The lower alkoxy group is an alkoxy group having 1 to 3 carbon atoms, and specifically includes a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and the like.
[0014]
Next, n in the general formula (1) is 5 to 30, preferably 9 to 20. M represents 3 to 300, preferably 3 to 150.
[0015]
Representative examples of the organic phosphorus compound represented by the general formula (1) according to the present invention include, for example, tri (ethylene glycol) (methyl) diphenylphosphinodecyl ether, dodeca (ethylene glycol) (methyl) diphenylphosphino Decyl ether, poly (ethylene glycol) (methyl) diphenylphosphinodecyl ether, poly (ethylene glycol) (methyl) diphenylphosphinooctadecyl ether, poly (ethylene glycol) (methyl) dibutylphosphinodecyl ether, poly (ethylene glycol) Diethylphosphinooctadecyl ether, dodeca (ethylene glycol) (isopropyl) dicyclohexylphosphinopentadecyl ether, poly (ethylene glycol) phenylmethylphosphinooctadecyl ether Ter, poly (ethylene glycol) (methyl) diethoxyphosphinoundecyl ether, poly (ethylene glycol) (methyl) di (butylphenynoxy) phosphinodecyl ether, poly (ethylene glycol) (methyl) diphenylphosphinophenyl Examples include decyl ether.
[0016]
The organophosphorus compound represented by the general formula (1) is, for example, the general formula (2).
R ¹ R ² PM (2)
(Wherein M represents an alkali metal) and the following general formula (3)
XA (CH ₂ ) _n (OCH ₂ CH ₂ ) _m R ³ (3)
(Wherein X represents a halogen atom) and can be produced by reacting with an ω-substituted halide in an approximately equimolar amount.
[0017]
As described above, the organophosphorus compound (water-soluble ligand compound) of the general formula (1) is a parent in which a phosphorus atom and a polyethylene glycol hydrophilic moiety are bonded by a long-chain alkylene group or a long-chain alkylenephenylene group. Since it is a compound exhibiting hydrating properties, when it is mixed with a Group 8 transition metal complex, a catalyst that smoothly proceeds the hydroformylation reaction in an aqueous solution can be obtained.
[0018]
Since the catalyst according to the present invention contains the above-mentioned specific components, as a raw material for the hydroformylation reaction, a water-insoluble long-chain alkene that has been conventionally difficult to synthesize, such as 1-octene, 1-dodecene, etc. Even if it is used, the corresponding aldehydes can be obtained in high yield and high selectivity without using other additives in combination.
[0019]
The Group 8 transition metal complexes used in the present invention include metal salts, hydrates and homo- or hetero-binuclear complexes thereof. The group 8 transition metal complex is preferably a rhodium complex, cobalt complex, iridium complex, ruthenium complex or platinum complex, more preferably a rhodium complex, cobalt complex or iridium complex.
[0020]
Examples of Group 8 metal complexes used in the present invention include rhodium trichloride, rhodium acetate, tris (acetylacetonato) rhodium, (acetylacetonato) dicarbonylrhodium, (acetylacetonato) (1,5-cyclohexane). Octadiene) rhodium, (acetylacetonato) (bicyclo [2.2.1] hepta-2,5-diene) rhodium, tetracarbonyldi-μ-chlorodirhodium, chloro (1,5-cyclooctadiene) rhodium dimer, Bis (bicyclo [2.2.1] hepta-2,5-diene) chlororhodium dimer, chlorobis (cyclooctene) rhodium dimer, μ-dichlorotetraethylenedirhodium, dodecacarbonyltetrarhodium, hexadecacarbonylhexorhodium, hydridotetracarbonyl Rhodium, octacarbonyl dicobalt, dodecacarbonyl tetraco Balto, tetracarbonyl (η-butadiene) dicobalt, hexadecacarbonyl hexacobalt, dodecacarbonyl hydrido tricobalt ruthenium, hydrido tetracarbonyl cobalt, dicarbonyl (η-cyclopentadienyl) cobalt, dodecacarbonyl hydrido tetrairidium, hexadeca Carbonyl hexairidium, chlorotricarbonyliridium, di-μ-chlorotetrakis (cyclooctene) iridium, di-μ-chlorotetrakis (ethylene) iridium, di-μ-chlorobis (1,5-cyclooctadiene) iridium Etc.
[0021]
The catalyst according to the present invention can be purified by mixing and adjusting the group 8 transition metal complex and the organophosphorus compound (water-soluble ligand compound) represented by the general formula (1) in the reaction system. It may be used as it is without being purified.
The mixing ratio of the metal complex and the organic phosphorus compound (water-soluble ligand compound) in this reaction catalyst system is the equivalent ratio of the group 8 transition metal atom and the phosphorus atom of the organic phosphorus compound (water-soluble ligand compound). The phosphorus atom is 1 to 100, preferably 2 to 30 with respect to the Group 8 transition metal atom 1.
[0022]
When carrying out the reaction, usually only water is used as a reaction solvent, but a general organic solvent may be used together. In the case of using an organic solvent, aromatic hydrocarbons such as toluene and xylene, ethers such as diethyl ether, dibutyl ether and tetrahydrofuran, and aliphatic saturated hydrocarbons such as pentane and hexane can be used.
[0023]
Separation of the product after the reaction is easily carried out by an ordinary purification and isolation method such as distillation and recrystallization after separating the organic layer as the product from the aqueous layer containing the catalyst. The aqueous layer containing the catalyst can be used as it is in the subsequent hydroformylation reaction.
[0024]
【Example】
Next, the present invention will be described more specifically with reference to examples.
[0025]
Example 1
Diphenylphosphine (2.58 mmol) is added to a solution of t-butoxypotassium (2.85 mmol) in tetrahydrofuran (10 ml), and the mixture is stirred at room temperature for 4 hours. Tri (ethylene glycol) (methyl) 10-bromodecyl ether (2.59 mmol) is added to the reaction solution, and the mixture is stirred at room temperature for 10 hours. When 20 ml of pentane is added to the reaction solution and the precipitate is filtered and then distilled, tri (ethylene glycol) (methyl) 10-diphenylphosphinodecyl ether (compound A) represented by the following formula is obtained in 69% yield. It was.
Ph ₂ P (CH ₂ ) ₁₀ (OCH ₂ CH ₂ ) ₃ OMe (Compound A)
[0026]
Next, the spectrum of Compound A is shown.
1H-NMR: 1.17-1.34 (m, 10H, CH ₂ ), 1.34-1.48 (m, 4H, CH ₂ ), 1.56 (tt, J = 7.0, 7.0 Hz, 2H, CH ₂ ), 2.00-2.06 (m , 2H, CH ₂ P), 3.37 (s, 3H, CH ₃ O), 3.43 (t, J = 7.0 Hz, 2H, CH ₂ O), 3.53-3.60 (m, 4H, OCH ₂ CH ₂ O), 3.62-3.70 (m, 8H, OCH ₂ CH ₂ O), 7.27-7.35 (m, 6H, C ₆ H ₅ ), 7.35-7.44 (m, 4H, C ₆ H ₅ ). 13C-NMR: 26.00 (d , J = 16.5Hz), 26.12, 28.08 (d, J = 11.3 Hz), 29.28, 29.48, 29.51, 29.58, 29.66, 31.26 (d, J = 13.4 Hz), 59.10, 70.09, 70.57, 70.63, 70.67, 71.58 , 71.98, 128.41 (d, J = 11.4 Hz), 128.42, 132.73 (d, J = 18.6 Hz), 139.07 (d, J = 12.4 Hz). 31P-NMR: -16.1. HRMS calcd for C ₂₉ H ₄₅ O ₄ P 488.3053, found 488.3082. Anal.calcd for C ₂₉ H ₄₅ O ₄ P: C, 71.28; H, 9.28; found: C, 71.37; H, 9.47.
[0027]
Example 2
Diphenylphosphine (2.06 mmol) is added to a solution of t-butoxypotassium (2.02 mmol) in tetrahydrofuran (10 ml) and stirred at room temperature for 4 hours. Poly (ethylene glycol) (methyl) 18-bromooctadecyl ether (number average molecular weight 1100, 2.00 mmol) is added to the reaction solution, and the mixture is stirred at room temperature for 10 hours. When the reaction solution was concentrated and subjected to column purification, poly (ethylene glycol) (methyl) 10-diphenylphosphinooctadecyl ether (Compound B) having a number average molecular weight of 1207 represented by the following formula was obtained.
Ph ₂ P (CH ₂ ) ₁₈ (OCH ₂ CH ₂ ) _n OMe (n = 16.8) (Compound B)
[0028]
Example 3
Diphenylphosphine (3.06 mmol) is added to a solution of t-butoxypotassium (3.02 mmol) in tetrahydrofuran (10 ml) and stirred at room temperature for 4 hours. Poly (ethylene glycol) (methyl) 10-bromodecyl ether (number average molecular weight 792, 3.01 mmol) is added to the reaction solution, and the mixture is stirred at room temperature for 10 hours. When 20 ml of pentane was added to the reaction solution and the precipitate was filtered and purified by column purification, poly (ethylene glycol) (methyl) 10-diphenylphosphinodecyl ether (Compound C) having a number average molecular weight of 897 represented by the following formula was found to be 83. % Yield was obtained.
Ph ₂ P (CH ₂ ) ₁₀ (OCH ₂ CH ₂ ) _n OMe (n = 12.3) (Compound C)
[0029]
Next, the spectrum of Compound C is shown.
1H-NMR: 1.17-1.33 (m, 10H, CH ₂ ), 1.34-1.45 (m, 4H, CH ₂ ), 1.50-1.59 (m, 2H, CH ₂ ), 1.97-2.08 (m, 2H, CH ₂ P), 3.36 (s, 3H, CH ₃ O), 3.37-3.45 (m, CH ₂ O), 3.49-3.71 (m, 49.2H, OCH ₂ CH ₂ O), 7.27-7.35 (m, 6H, C ₆ H ₅ ), 7.35-7.44 (m, 4H, C ₆ H ₅ ). 31P-NMR: -16.1.
[0030]
Example 4
Dibutylphosphine (2.98 mmol) is added to a tetrahydrofuran (10 ml) solution of t-butoxypotassium (3.01 mmol), and the mixture is stirred at room temperature for 4 hours. Poly (ethylene glycol) (methyl) 10-bromodecyl ether (number average molecular weight 792, 3.01 mmol) is added to the reaction solution, and the mixture is stirred at room temperature for 10 hours. When the column is purified by adding 20 ml of pentane to the reaction solution and filtering the precipitate, poly (ethylene glycol) (methyl) 10-dibutylphosphinodecyl ether (compound D) having a number average molecular weight of 857 represented by the following formula is obtained. It was.
Bu ₂ P (CH ₂ ) ₁₀ (OCH ₂ CH ₂ ) _n OMe (n = 12.3) (Compound D)
[0031]
Example 5
The autoclave is charged with (acetylacetonato) dicarbonylrhodium (0.015 mmol), compound A (0.048 mmol) and water (2 ml) 1-octene (1 ml, 6.37 mmol). A 1: 1 mixed gas of carbon monoxide and hydrogen is pressurized at 1 MPa and stirred at 100 ° C. for 3 hours. After returning to normal pressure, the supernatant was taken and distilled to obtain nonylaldehyde in a yield of 47% (n- / iso- = 51/49).
[0032]
Example 6
An autoclave is charged with (acetylacetonato) dicarbonylrhodium (0.015 mmol), compound C (0.051 mmol) and water (2 ml) 1-octene (1 ml, 6.37 mmol). A 1: 1 mixed gas of carbon monoxide and hydrogen is pressurized at 1 MPa and stirred at 100 ° C. for 3 hours. After returning to normal pressure, the supernatant was taken and distilled, and nonylaldehyde was obtained in 61% (n- / iso- = 71/29) yield. When 1-octene (1 ml, 6.37 mmol) was added to this reaction solution (aqueous layer) and the reaction was carried out under the same conditions, nonylaldehyde was obtained in 57% (n- / iso- = 76/24) yield. .
[0033]
Example 7
The autoclave is charged with (acetylacetonato) dicarbonylrhodium (0.015 mmol), compound C (0.054 mmol) and water (2 ml) 1-octene (1 ml, 6.37 mmol). A 1: 1 mixed gas of carbon monoxide and hydrogen is pressurized at 3 MPa and stirred at 100 ° C. for 3 hours. After returning to normal pressure, the supernatant was removed and distilled, and nonylaldehyde was obtained in a yield of 80% (n- / iso- = 72/28). When 1-octene (1 ml, 6.37 mmol) was added to this reaction solution (aqueous layer) and the reaction was carried out under the same conditions, nonylaldehyde was obtained in a yield of 74% (n- / iso- = 72/28). . Furthermore, when 1-octene (1 ml, 6.37 mmol) was added to this reaction solution (aqueous layer) and the reaction was conducted under the same conditions, nonylaldehyde was obtained in 87% (n- / iso- = 71/29) yield. It was.
[0034]
【The invention's effect】
The organophosphorus compound of the present invention is a novel compound not described in any literature, and as is clear from the chemical structural formula represented by the general formula (1), a phosphorus atom and a polyethylene glycol hydrophilic moiety are long-chain alkylene groups. Alternatively, it is an amphiphilic compound bonded with a long-chain alkylenephenylene group.
In addition, since this compound has a hydrophilic group at one end of the molecule and a phosphorus atom that coordinates the catalyst at one end of the hydrophobic group, as is clear from the structural characteristics of the compound, phosphorous is present in the reaction system. The atomic portion is likely to be present on the organic layer side, and further, it is presumed that the solubility in water becomes low at the reaction temperature of the hydroformylation reaction and is likely to exist on the organic layer side.
Therefore, when this is mixed with the Group 8 transition metal complex, a catalyst that smoothly proceeds the hydroformylation reaction in an aqueous solution can be obtained.
In addition, since the catalyst according to the present invention contains the above-mentioned unique components, it is a water-insoluble long-chain alkene that has been conventionally difficult to synthesize, such as 1-octene, 1-octene, as a raw material for the hydroformylation reaction. Even if dodecene or the like is used, the corresponding aldehydes can be obtained with high yield and high selectivity without using other additives.

Claims (3)

The following general formula (1)
R ¹ R ² PA (CH ₂ ) _n (OCH ₂ CH ₂ ) _m R ³ (1)
(In the formula, R ¹ and R ² is an alkyl group, an aryl group, an aralkyl group, an alkoxy group or an aryloxy group, R ¹ and R ² may combine to form a ring, R ³ is , A hydroxyl group and a lower alkoxy group, A represents a phenylene group or a methylene group, n represents 5 to 30, and m represents 3 to 300). A hydroformylation reaction catalyst comprising an organophosphorus compound represented by the general formula (1) and a Group 8 transition metal complex. The hydroformylation reaction catalyst according to claim 2, wherein the organophosphorus compound represented by the general formula (1) is coordinated to a Group 8 transition metal complex.